HYDROCRACKING OF WASTE PLASTICS T O CLEAN LIQUID FUELS Weibing Ding, Jing Liang and Larry L.

Anderson 3290 ME9 Department of Chemical and Fuels Engineering University of Utah Salt Lake City, UT 841 12 Keywords: hydrocracking, waste plastics, liquid fuels ABSTRACT Recycling of waste plastics and other packaging materials is becoming more necessary since they represent a readily available source of fuels and/or chemicals and a growing disposal problem. One way of accomplishing such recycling is to convert these waste polymers into transportation fuels by thermal and/or catalytic processing. In recent work thermal processing was found to be easily accomplished. However, the products were not of sufficiently high quality to be used as transportation fuels without extensive upgrading. Waste materials from the U.S. (American Plastics Council) and Germany (Duales System Deutchland or DSD) were processed by hydrocracking, Commercial catalysts, KC-2001 and KC-2600 were used in hydrocracking experiments using 27 ml tubing reactors. Effects of reaction temperature, hydrogen pressure, and reaction time on product yields and quality were studied. The liquid products were subjected to detailed analysis by GC, GCiMS, and TGMS. Possible reaction mechanisms will be proposed based on the analytical data. Other bifunctional catalysts developed in our laboratory were also tested and results will be compared with those obtained using the mentioned commercial catalysts. INTRODUCTION Conversion of waste plastic to clean liquid fuels has been widely studied all over the world recently [1,2]. Most bench scale and pilot plant studies employed two-stage processes, i t . , in the first stage, plastic is thermally degraded to crude oil-like liquid products, and the liquids are subjected to further catalytic cracking to produce gasoline-like products in the second stage. This process may be more costly than a single stage processing, is., direct conversion of waste plastic to gasoline-like products [3]. The challenge of the latter is to utilize high efficiency catalysts. Pure polymers, such as high density polyethylene, polypropylene, polystyrene, etc., are different than waste plastics which contain some nitrogen, sulfur, and even chorine, as well as impurities. These compounds are believed to be poisonous to some catalysts which were effective in cracking pure polymers. Therefore, a catalyst with not only hydrocracking-hydrogenation ability, but also hydrodenitrogenation-hydrodesulfurization function is needed for directly converting waste plastics to clean liquid fuels. In this study, two commercial hydrocracking catalysts (KC-2001 and KC-2600), obtained from Akzo Nobel Chemical, Inc., were used for hydrocracking two different kinds of waste plastics; one fiom the American Plastics Council (APC plastic) and the other from Germany's Duales System Deutschland @SD plastic). A catalyst (Ni supported on a mixture of zeolite and silica-alumina) made in this lab was also tested and the results are compared.

EXPERIMENTAL APC plastic, obtained from the American Plastics Council, was ground to -8 mesh. Detailed analyses of this plastic are listed elsewhere [4]. DSD plastic, obtained from Germany's Duales System Deutchland, was used as received except for d f i g before reaction. The results of ultimate and proximate analyses are listed in Table 1, whereas the results of ash analyses are listed in Table 2 151. HZSM-5 and Si02-Al203 (with 13% A I 2 0 3 content), were purchased from United Catalysts Inc. and Aldrich Chemical Company, respectively. The average pore size and surface area of the Si02-A1203were 65 A and 475 m2/g respectively; while those of the HZSM-5 were 6.2 A and ca. 200 m2/g respectively. The metal salts, nickel @I) nitrate hexahydrate was obtained from Aldrich Chemical Company. KC-2001 and KC-2600 were obtained from Akzo Nobel Chemicals, Inc., whereas as Ni/HSiAl (HSiAl is a mixture of four parts by weight of silica-alumina and one part by weight of HZSM-5) was prepared in this lab. All three catalysts were presulfided before reaction [6]. Hydrocracking reactions of DSD and APC plastics were carried out in a 27 ml tubing reactor at 375 to 480'C for 60 minutes. Typically, 2 g of plastic and a calculated amount of presulfided catalyst, if any, were fed into the reactor, which was then closed, purged with nitrogen,
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and then pressurized with hydrogen to the desired initial pressure, usually 1000 psig. The reactor was then immersed into a preheated fluidized sand bath and reached the desired reaction temperature within 3 to 4 minutes, The mixing of reactants and catalyst particles was achieved by horizontal shaking of the reactor at 160 rpm. Detailed reaction procedure and definitions of yields have been reported elsewhere [7].

The gases obtained from the first stage were analyzed by a flame ionization detector by gas chromatography (I-IP-589011) using a column packed with HayeSep Q. The liquid products were analyzed by W/MS using a 30-mlong DB-5 capillary column. The boiling point distribution of the liquid products were determined by simulated distillation according to ASTh4 D 2887-89 and D5307-92. The analysis was performed on a HP-5890 series II gas chromatograph, using a Petrocol B column (6 inches long and 0.125 inches outside diameter).
RESULTS AND DISCUSSION Hydrocracking of APC Plastic. Some 99% conversion was obtained when APC plastic i was noncatalytically degraded at 435C or at 480C [7,8]. However, the quality of ol products obtained was far below that of commercial premium gasoline. Hydrocracking catalysts, KC-2600 and Ni/HSiAI, were effective for degradation of AFT plastic at 375OC (Figure 1). The conversion was markedly increased in the presence of the mentioned catalysts. Figure 2 shows the Wh4S profile of oil products obtained over KC-2600. The oil contains mostly isoparaffins, some nparaffins, and small amounts of aromatics as well as cycloparaffins. This indicates that KC-2600 does have hydrocracking and hydroisomerization ability. The oil was also subjected to elemental analysis and no nitrogen and sulfur was detected, suggesting HDN and HDS ability of the catalyst. [61. Hydrocracking of DSD Plastic. DSD plastic can be hydrocracked thermally to produce gaseous and Liquid products. Figure 3 shows the effect of reaction temperature on thermal hydrocracking of this plastic. The conversion was not a function of temperature in the temperature range of 450 to 480"C, although conversion increased markedly with temperature increasing from 370 to 450C. Different from the APC plastic, this DSD plastic contained about 4.4% ash. Therefore, the maximum conversion should be about 95% and this value was reached at temperatures higher than 450OC. The maximum yield liquid was also obtained at 450C. indicating further thermal cracking to form smaller size molecules, such as gases, at temperature higher than 450C. It is reasonable to suggest that 4 5 0 T is the optimum temperature for thermally converting DSD plaitic to liquid products. The oil products obtained at 430, 450, and 480OC were subjected to simulated distillation analyses and the results are shown in Figure 4. Not surprisingly, the oil obtained at higher reaction temperatures was lighter than that obtained at lower temperature. The liquids need further treatment for use as transportation fuels, such as gasoline. The effects of catalysts on hydrocracking of DSD plastic are shown in Table 3. At 375"C, only about 10% conversion was achieved for thermal reaction, however, the conversion reached 66.7% when 40% KC-2001 was added (Figure 3 and Table 3). The effects of the catalysts decreased in the order: KC-2001 > NiRISiAl> KC-2600. It is noteworthy that conversion of APC plastic reached over 90% in the presence of KC-2600 or Ni/HSiAI (Figure I), whereas only 3050% conversion were obtained for DSD plastic at the same reaction conditions(Tab1e 3). The analyses showed that the main difference between APC plastic and DSD plastic was that the latter contained some chlorine, more ash, and some waste paper (Table 1). These materials may have some negative effects on these catalysts at the conditions used. The conversion of DSD plastic was enhanced when temperature was increased to 4OOOC and the amount of catalyst was decreased to 20% (Table 3). Some 80% conversion was obtained over 20% KC-2001 at 400C. Additional experiments showed that about 94% DSD plastic was converted to gaseous and liquid products over 40% KC-2001 at 400'C. This indicates that KC-2001 may be a suitable catalyst for hydrocracking of DSD plastic to liquid fuels. CONCLUSIONS APC plastic can be converted totally to liquids and gases at 375C in the presence of a hydrocracking catalyst, Ni/HSiAI or KC-2600. The quality of the liquid products obtained was close to that of a commercial premium gasoline. Catalytic hydrocracking of DSD plastic at the m e conditions was found to be more difficult than that of APC plastic. This may be due to the negative effects of some impurities contained in DSD plastic, such as chlorine, ash, and paper. At 400C, DSD plastic can be nearly totally converted to gaseous and liquid products with 40% KC2001 catalyst. The products obtained will be analyzed hrther.
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Thermal hydrocracking of DSD plastic is feasible, and the optimum reaction temperature was found to be 450OC. At this condition, DSD plastic can be totally converted and the yield of liquid products can reach as high as some 60%.

ACKNOWLEDGMENT
The authors gratehlly acknowledge the hnding support f?om the US. Department of Energy through the Consortium for Fossil Fuel Liquefaction Science.

REFERENCES
1. DAmico, E.; Roberts, M. (1995), Chem. Week, Oct. 04,32. 2. Frankenhaeuser, M, Inverardi, M.; Mark, F.; Martin, R.; Soderberg, D. (1995), Summary Report of Association of Plastics Manufactures in Europe, EKONO Energy Ltd. 3. Songip, A. R.; Masuda, T.; Kuwahara, H.; Hashimoto, K. (1990), Energy and Fuels, 8, 1238. 4. Ding, W.; Liang, J.; Anderson, L. L.(1996). Fuel Process. Tech., 49,49-63. 5. Huffman, G. P.; Shah, N. (1996), University ofKentucky. 6. Ding, W.; Liang, J.; Anderson, L. L. (1997), Energy and Fuels, submitted. 7. Ding, W.; Liang, J.; Anderson, L. L. (1 997), Fuel Process. Tech., 5 I, 47-62. 8. Ding, W.; Liang, J.; Anderson, L. L. (1997), Preprints of ACS, Div. Petro. Chem., 42(2), 428432.

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Table 1, Proximate and Ultimate Analyses of DSD Plastic

Wt%

Proximate analysis Moisture Ash Volatile matter Fixed carbon Ultimate analysis Carbon Hydrogen Nitrogen
Chlorine

0.16 4.44 93.n 1.08 78.96 13.5 0.67 1.26

0.08

Sulfur

Table 2. Ash Analyses of DSD Plastic (by ICP)

wi%

Al As
Be Ca

10.0
4 0 PPm <1 PPm

cd
cn Cr cu Fe
K Mg Mn Mo Na Ni Pb Se Si Ti V

13.0 <I PPm 26 ppm 0.08

0.02

3.5

1.85 2.05 0.08 40 PPm

3.9 0.01 0.01 4 0 PPm

18.0 12.8 21 ppm

Ni/HSiAI, 40%

I
Ni/HSiAI, 20%
1-

No Catalyst

20

40

60

80

100

Yields, wt% HConversion PLiquid Yield E4 G s Yield a

Figure I. Results of degradation of APC plastic in a 27 ml tubing reactor at 375C. 1000 psig H (initial), for a reaction time of 1 h with the indicated catalysts. ,

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TIC: 96HP238.D
3000000

2000000

isooooa

ioouuoa

5ooooc

!n:_2.00

4.00

6.00

0.00

7 T - . , , . . . , . . . I . . . . , . 10.00 12.00 1 4 . 0 0 16.00 1 8 . 0 0 2 0 . 0 0

.2 2 .,0.0 . .2 . .,0 0 . .2 . .,0 0 . . 4 6

Figure 2. GCMS analyses of the oil products obtained from hydrocracking of APC plastic in a 27 ml tubing reactor at 375"C, 1000 psig H2(initial), for a reaction time of 1 h with 40% KC-2600

100,

90 - 80 --

70 -$

.p?

60 - 50 - -

vi

40

--

30 -20 - IO -O T

350

375

400

425

450

475

500

Reaction Temperature,"C. Figure 3. Effect of reaction temperature on thermal hydrocracking of DSD plastic (reaction conditions: 27 ml tubing reactor, 1000 psig H (initial), 60 minutes, 160 rpm) ,
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',

//
'"T Y
0 100
200

Oil Obtained at 48OoC

300

400

500

600

700

Boiling Point, "C

Figure 4. Boiling point distribution of oils obtained from thermal hydrocracking of DSD plastic at 1000 psig Hz(initial), 60 minutes

Table 3. Results of Catalytic Hydrocracking of DSD Plastic in a 27 ml Tubing Reactor at 1000 psig H2 (initial), for a Reaction Time of 60 Minutes. Catalyst
375C

Gas Yield, wt%

Oil Yield', wtYo

Conversionb,wt%

KC-200 1'. 40% KC-2600'. 40% N/HSiAl. 40%

35.7

31.0

66.7

10.2
14.8

20.7
35.1

30.9 49.9

400'C

KC-2001', 20% KC-2600', 20% N i S i A I , 20%

a

39.9

38.8

78.7 63.4

15.2 20.0

48.2
45.5

65.5

n-pentane soluble; Conversion (wt%) = lOO(1-weight of pentane insolubledweight of feed); ' Catalysts, obtained from Akzo Nobel Chemicals Inc., may contain NiMo/AI2O3and/or NiMo/zeolite.

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